Manufacture of hydrocarbons



Patented June 25, 1935 x l I 2,005,861

' UNITED T STATES PATENT OFFICE MANUFACTURE OF HYDROOABBONS Vladimir Ipatieif, Chicago, 111., aosignor to Universal Oil Products Company,- Chicago, 111., a corporation of Delaware No Drawing. Application January 18, 1933,

Serial No. 852,009

Claims. ,(Oi. 260-168) This invention relates'mor particularly to the I am aware that the "alkylation of aromatic manufacture of hydrocarbons of suitable boilhy r ar ns y fins n the Presence of Such ing point for use as components of gasoline mixcatalytic condensing agents as sulfuric acid, alt uminum chloride, etc., is known. When using 5 In a more specific sense the invention has refthese powerful reagents, however, there is a con- 0 erence to a process which both conserves matesiderable tendency for the more reactive oleilns rials which are ordinarily considered as waste such as di-oleflns and certain'iso oleflns to unproducts in cracking processes and at the same dergo polymerization in preference to adding to time produces hydrocarbons having specially the aromatic rings to produce alkylderivatives.

high anti-detonating characteristics. The extent of the polymerization reactions may 10 Owing to the adoption of high compression be considerable and frequently involve the proratios in automobile engines to increase their duction of both materials boiling too high for thermodynamic efllciency, a demand has been use in gasoline and in addition polymers of such made upon t eum refining n other high molecular weight that they are of a gummy st which ish dr c motor uel or resinous character. While the relative 15 for fuels of a hi h an kn o o l wn amounts of polymerization and alkylation may character. The cra kin pro which generallyv be controlled to a certain extent by conditions of produces both unsaturated hydrocarbons a operation, particularly in regard to temperature, oyohe (i i aromatic) hydrocarbons due to such control is not always satisfactory and the the dehydrogenating Character of the deeompresent process is offered as ameans of enabling 20 p sition rea i ns i employed quite generally to better control 01 alkylation reactions and conmeet the demand for ahigh antlknock motor fuel. servation of t more reactive and readily poly- However, complete co t ol of e proportion of merizable materials. aromatics to olefin is o always P as The reactions between oleflns and aromatics the character of the ehel'glng oi1 Varies h the in the presence of condensing catalysts are bas- 25 ype o crude oil fremwhieh they are Produced, ically of a simple character, although there is and when intensive cracking conditions are "emalways a certain amount of side reactions tp y in an effort to increase the amount of ing in loss of acid and oxidation of the hydroaromat os a hence the ahtikhoek Value carbons. Apparently the intermediate-comdesirably la losses in 8 d eekevmay be pound theory of catalysis bestexplains reactions 30 encountered and frequently the amount of oleflns' which means, in the present instance, that both particularly those of a highly unsaturated and types reacting'components form transient addh unstable characten nay increase roughly in prohon compounds with the catalysts which Portion to the increase in aromatics; ther react to produce the synthetic hydrocar- The fixed gases produced in crackmg Processes bon and regenerate the catalyst. The reaction 35 contain notable amounts or olefins Including which takes place when iso-butylene is reacted ethylene, propylene, the butylenes and other gas with benzol in the presence of phosphoric acid is of a more highly unsaturated and still more reactive character such as acetylene, butadienes, in pomt and may be expressed by h following 4 etc. Extensive experimenting has been conductequation 0 ed to find ways of utilizing the reactive .con- C H +C H H230 H C stituents of gases from cracking plants and con- I b 4 0 B a ,1 ISO-l t ,1 vert them into more valuable products. For ex- Y ample, the process of manufacturing iso-propy1- This equation ShOWS the union of one molecule ,and other alcohols from the olefins present in eeehof yl n and benzol. The reactions 45 cracked gases has reached commercial propormay proceed further to the P uc n of the tions and the manufacture of glycol from ethyldiand even tri-alkyl derivatives depending upon e 1 al o practiced, The present process conditions of operation and the relative properables the effective utilization of the more reactive tions of olefins and aromatics- 0 oleiinic constituents of cracked gases and similar In conductin operatio s ead o e prooleflns produced in any manner. duction of hydrocarbons according to the proc- In one specific embodiment the present iness of the present invention, oleiins either indivention comprises treatment of aromatic or simvidual or in admixture with other reactive ole;- ilarly reactive cyclic hydrocarbons with oleflnic fins or paraffinic gases may be introduced into gases in the presence of phosphoric acid catalyst. a well agitated mixture of liquid aromatic hydro- 5 -mad phosphoric acid. Moderately superatmospheric temperatures are suitable such as those in the neighborhood of 60 C. in the case oftheolefinspresentinsuchcommercialgas mixtures as. those encountered in oil cracking processes. It is preferred to use relatively conmodified to permit the use of ordinary batch and continuous treating plants which are familiar to petroleum refinery operators. For example, a mixture of phosphoric acid and aromatic oil may be circulated by centrifugal pumps taking suction at the bottom of a batch agitator and discharging back into the top. Such operation may be conducted to permit the separation and continuous removal of alkylated aromatics and if necessary the recycling of the gases.

As a further alternative method of operation, an olefinic gas mixture, for example, the fixed gases from an, oil cracking plant, the requisite amount of aromatic oil and phosphoric acid may be injected into a suitable mixer positioned'in the upper portion of a treating tower containing filling or spacing material, all reacting components passing downwardlythrough the interstices to effect substantially complete reaction. The gases denuded of reactive olefins may be separated in subsequent receivers and the acid and liquid hydrocarbon layers either returned to the treater or finally removed. As a general rule the acid may be cycled for a long time before it is contami- Bensol.

nated to an extent rendering its use uneconomical.

The process may be operated in conjunction with the use of more powerful condensing reagentssuch as sulfuric acid or aluminum chloride which are employed in a second step to effeet the addition of the residual olefins in the gas mixtures from the process to fresh quantities ofaromatics or to the partially alkylated product of the process. Owing to the great variations in the composition of gases from cracking processesit' is evident that a variety of alkylated products is made possible and that the separate products may be held for blending with different gasolines which need different amounts of high antlknock blending materials to raise them up to any desired standard.

It is evident that on account of the large number of olefins on the one hand and aromatics on the other which may be reacted to form mixed hydrocarbon derivatives when using the catalyst products of e "lene. The bensol was substan-- tially the pure compound. The gaseous olefin mixture was passed into a thoroughly agitated mixture of benzol and phosphoricacid in the ratio of approximately two volumes of benzol to one of acid, with the temperature maintained at about 00 C.

The following table shows the distillation range and the refractive index of the cuts obtained along with the ultimate analyses and specific gravity of two selected fractions:

The following table, showing the physical constants of certain individual hydrocarbons which would normally be expected to be present in such a mixture as the above is'given to permit intercomparison and identification of fractions.

' Turns #11 Physical constants of pure components Analyses Np" f d 4001 ca: 1.1 can 4on0 au 14.: 0.115 (t) m *1 ii: (iii Di(t)butylbensol sec 11.0

closely approximates an equal mixture of mono-- (t)butyl benzene and tri-iso-butylens:

Tan: 111

Constants of 50/50 mixture of moao(t)batwlbenround in Cals'd -1700.

ihctlon In further substantiation of the alkylation reactions, a definite quantity of tertiary di-butyl benzol was isolated from the redistilled fraction. From the foregoing it is evident under the conditions used that alkylation and polymerisation reactions proceeded with approximately equal velocity. The product shown in table #1 had an antiknock value greatly in excess of that of isooctane and could be blended in any proportion with low antiknock value gasoline to improve its q lity. v I

The foregoing specification has set forth the nature of the present invention and the numerical data given is sufiicient to show its utility.

However, many other examples might be given and the invention is not to be unduly limited in its generally broad scope by the specific data presented.

I claim as my invention:

1. In the art of alkylation, the method which comprises reacting a hydrocarbon of the benzene series boiling within the gasoline range with a gaseous olefin in the presence of a phosphoric acid catalyst under conditions to produce a substantial quantity of alkylated derivatives within the gasoline boiling range, and recovering the gasoline boiling derivatives thus formed.

2. In the art of alkylation, the method which comprises treating an aromatic hydrocarbon of the benzene series boiling within the gasoline range in the presence of a phosphoric acid catalyst, with the olefinic gas mixture produced in the cracking of hydrocarbon oil, reacting oleflns contained in the gas mixture with the aromatic hydrocarbon under conditions to produce a substantial quantity oi. alkylated derivatives within the gasoline boiling range, and recovering the gasoline boiling derivatives thus formed.

3. In the art of alkylation, the method which comprises treating an aromatic hydrocarbon oi. the benzene series boiling within the gasoline range in the presence of a phosphoric acid catalyst, with the olefinic gas mixture produced in the cracking of hydrocarbon oil, reacting olefins contained in the gas mixture with the aromatic hydrocarbon at a temperature not substantially v above 0., to produce a substantial quantity of alkylated derivatives within the gasoline boiling range, and recovering the gasoline boiling derivatives thus formed.

4. A process for producing anti-knock compounds suitable as components oif motor fuel, which comprises reacting .a hydrocarbon of the benzene series boiling within "the gasoline range with a gaseous olefin in the presence of a phosphoric acid catalyst at a temperature not substantially in excess of 60 C.

5. A process for producing anti-knock compounds suitable as components of motor Iuel, which comprises reacting benzol with a gaseous olefin at a temperature not substantially above 60 and in the presence of a catalyst consisting 

